Acceptorless dehydrogenation(AD) that uses non-toxic reagents and produces no waste is a type of catalytic reactions toward green chemistry.Acceptorless alcohol dehydrogenation(AAD) can serve as a key step in constructing new bonds such as C-C and C-N bonds in which alcohols need to be activated into more reactive ketones or aldehydes.AD reactions also can be utilized for hydrogen production from biomass or its fermentation products(mainly alcohols).Reversible hydrogenation/dehydrogenation with hydrogen uptake/release is crucial to realization of the potential organic hydride hydrogen storage.In this article,we review the recent computational mechanistic studies of the AD reactions catalyzed by various transition metal complexes as well as the experimental developments.These reactions include acceptorless alcohol dehydrogenations,reversible dehydrogenation/hydrogenation of nitrogen heterocycles,dehydrogenative coupling reactions of alcohols and amines to construct C-N bonds,and dehydrogenative coupling reactions of alcohols and unsaturated substrates to form C-C bonds.For the catalysts possessing metal-ligand bifunctional active sites(such as 28,45,86,87,and 106 in the paper),the dehydrogenations prefer the “bifunctional double hydrogen transfer” mechanism rather than the generally accepted β-H elimination mechanism.However,methanol dehydrogenation involved in the C-C coupling reaction of methanol and allene,catalyzed by the iridium complex 121,takes place via the β-H elimination mechanism,because the Lewis basicity of either the π-allyl moiety or the carboxyl group of the ligand is too weak to exert high Lewis basic reactivity.Unveiling the catalytic mechanisms of AD reactions could help to develop new catalysts. Acceptorless dehydrogenation (AD) that uses non-toxic reagents and produces no waste is a type of catalytic reactions toward green chemistry. A receptorless alcohol dehydrogenation (AAD) can serve as a key step in constructing new bonds such as CC and CN bonds in which alcohols need to be activated into more reactive ketones or aldehydes. AD reactions also can be utilized for hydrogen production from biomass or its fermentation products (mainly alcohols). Reversible hydrogenation / dehydrogenation with hydrogen uptake / release is crucial to realization of the potential organic hydride hydrogen storage.In this article, we review the recent work on chemical reactions of alcohols and amines to construct CN bonds, and dehydro genative coupling reactions of alcohols and unsaturated substrates to form CC bonds. For the catalysts possessing metal-ligand bifunctional active sites (such as 28, 45, 86, 87, and 106 in the paper), the dehydrogenations prefer the "bifunctional double hydrogen Of the generally accepted β-H elimination mechanism. However, methanol dehydrogenation involved in the CC coupling reaction of methanol and allene, catalyzed by the iridium complex 121, takes place via the β-H elimination mechanism, because the Lewis basicity of either the π-allyl moiety or the carboxyl group of the ligand is too weak to exert high Lewis basic reactivity. Unveiling the catalytic mechanisms of AD reactions could help to develop new catalysts.